Four metallic alloys, namely 2205 duplex stainless steel (2205DSS), ZMG232, and stainless steels SS430 and SS304 are investigated for use as interconnects in solid oxide fuel cells (SOFCs). A La0.67Sr0.33MnO3–δ (LSMO) film is deposited on these metallic-alloy substrates using a pulsed-DC magnetron sputtering system in the reactive mode, leading to the formation of a cubic perovskite structure. The coated alloys are then subjected to oxidizing heat treatments in air at 600 °C, 700 °C, 800 °C, and 900 °C, and their microstructures as well as electrical resistances are evaluated. The electrical resistance measurements are performed at 800 °C, and the area-specific resistance (ASR) of the film-coated 2205DSS alloy is found to be less than that of the uncoated alloy. This is because a thick layer of Cr2O3 and a (Mn, Fe)Cr2O4 spinel phase layer are formed, and some divalent metallic ions migrate into the Cr2O3 layer. It is found that alloys coated with a thin film of LSMO are more suitable for use as metallic interconnects in SOFCs with intermediate-temperature operating ranges.